Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

• the invention relates to a biaxially oriented, hydrolysis-resistant film made from one Thermoplastics, the thickness of which is in the range from 0.5 to 12 ⁇ m.
• the slide contains at least one degassing-resistant hydrolysis stabilizer and stands out next to it low hydrolysis rate due to its good dielectric properties, in particular, it has a high dielectric strength.
• the hydrolysis stabilizer tends when heating the film only to a small gas evolution.
• the invention further relates to a process for the production of this film and its use, and from the film manufactured capacitors.
• Foils for the production of capacitors have to meet high demands with regard to their dielectric strength and dielectric absorption in order to ensure sufficient voltage resistance in the capacitor and to heat up only slightly during the charging and discharging process. As described, inter alia, in EP-A-0 791 633, this is ensured by the high purity of the raw materials used. Therefore, it is usually necessary to do without additives (exceptions are inorganic mineral additives such as the SiO 2 or CaCO 3 pigments and polymers with a very low dielectric constant, such as polystyrene, etc.) that are used, in order to reduce the electrical properties not affect negatively.
• inorganic mineral additives such as the SiO 2 or CaCO 3 pigments and polymers with a very low dielectric constant, such as polystyrene, etc.
• polyethylene terephthalate In conventional film capacitors made of thermoplastics usually come Polyethylene terephthalate or polyethylene naphthalate homopolymers are used.
• polyethylene terephthalate tends to be at temperatures above Glass temperature and especially above 100 ° C for hydrolytic degradation. at are many areas of application for film capacitors, for example in the automotive sector Temperatures up to 130 ° C and sometimes even higher are not uncommon.
• PEN Polyethylene naphthalate
• PEN is indeed hydrolysis resistant, but has a significantly higher price and is therefore for most Areas of application uneconomical and builds after a long period of use with the above Temperatures also decrease significantly.
• the sensitivity to hydrolysis generally continues to increase on if instead of the homopolymers copolyesters such as polyethylene terephthalate (PET) with Isophthalic acid content are used.
• the layer capacitors described in the two applications have the cut surface increases gaps, which admittedly affect the electrical behavior of the Capacitors do not seem to interfere, but the processors too Lead to irritations and complaints.
• Hydrolysis stabilizers with low odor e.g. Block copolymers based of polycarbodiimides are known from DE 100 15 658 A1. However, the scriptures lead no foils or capacitors made from them.
• the object of the present invention is to overcome the described disadvantages of the prior art Avoid technology.
• the invention therefore relates to a biaxially oriented, hydrolysis-resistant film which contains a thermoplastic as the main component and has a thickness in the range from 0.5 to 12.0 ⁇ m, preferably 1.2 to 7.0 ⁇ m, and has an electrical dielectric strength AC of > 190 kV / mm and a roughness R a of ⁇ 150 nm and which contains at least one degassing-resistant hydrolysis stabilizer.
• the invention further relates to a method for producing this film and its use, and capacitors made from the film.
• the film according to the invention is characterized by its hydrolysis resistance, a low exhaust gas development when heated and high dielectric strength. Further it can be produced economically and is suitable for producing electrically stable ones Capacitors, which are also resistant to hydrolysis. It is also suitable for Manufacture of hydrolysis-resistant SMD capacitors. Such a capacitor, often used as an interference suppression capacitor, does not require a box, and therefore offers the advantage of one particularly small footprint and has a longer life than Capacitors made from unstabilized thermoplastics.
• the film according to the invention can also without losing its properties before coating, i.e. before the capacitor production.
• the Regenerate can thus be used again in the manufacturing process of the film.
• a high dielectric strength means that the dielectric strength (AC) of the film, measured according to DIN 53481 using the ball / plate method with AC voltage, one Value of ⁇ 190 kV / mm, preferably ⁇ 240 kV / mm and in particular ⁇ 280 kV / mm having.
• electrically stable capacitors means that those with the Capacitors equipped with hydrolysis stabilizers have a significantly longer service life own and have no high failure rates in practice compared to not capacitors equipped with hydrolysis resistance.
• the main component of the film is a thermoplastic.
• a thermoplastic for example, are suitable Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), bibenzene-modified polyethylene terephthalate (PETBB), bibenzene-modified Polybutylene terephthalate (PBTBB), bibenzene-modified polyethylene naphthalate (PENBB) or mixtures thereof, with PET, PEN and PETBB being preferred.
• PET Polyethylene terephthalate
• PEN polyethylene naphthalate
• PBT polybutylene terephthalate
• PBTBB bibenzene-modified polyethylene terephthalate
• PENBB bibenzene-modified polyethylene naphthalate
• DMT Dimethyl terephthalate
• EG ethylene glycol
• PG propylene glycol
• 1,4-butanediol Terephthalic acid
• TA Terephthalic acid
• NDA 2,6-naphthalenedicarboxylic acid
• IPA isophthalic acid
• c-CHDM, t-CHDM or c / t-CHDM trans- and / or cis-1,4-cyclohexanedimethanol
• c-CHDM, t-CHDM or c / t-CHDM other suitable dicarboxylic acid components (or Dicarboxylic acid esters) and diol components can be used.
• Polymers are preferred in which the dicarboxylic acid component is 95% and more, especially 98% and more consists of TA or NDA.
• Thermoplastics in which the diol component is 90% and more, in particular 93% and more consists of EG.
• the film according to the invention further contains inorganic or organic compounds which are required to adjust the surface topography.
• R a value a roughness
• the amount of the compounds used depends on the substances used and their particle size. The latter is in the range from 0.01 to 10.0, preferably 0.1 to 5.0 and in particular 0.3 to 3.0 ⁇ m.
• an R a value of und 150 nm and preferably of 100 100 nm is aimed for.
• the R a value is 100 100 nm and preferably ⁇ 70 nm, while for film thicknesses below 2.4 ⁇ m it is von 70 nm and preferably ⁇ 50 nm having.
• Suitable compounds for achieving the roughness are, for example, calcium carbonate, apatite, silicon dioxide, titanium dioxide, aluminum oxide, crosslinked polystyrene, zeolites and other silicates and aluminum silicates. These compounds are generally used in amounts of 0.05 to 1.5%, preferably 0.1 to 0.6%. The roughness can be easily determined depending on the connection used by simple mixing tests and subsequent measurement of the R a values.
• a combination of the silicon dioxide pigments 0.11% ®Sylysia 320 (Fuji, Japan) and 0.3% ®Aerosil TT600 (Degussa, Germany) results in an R a value of 70 nm for a 5 ⁇ m film Film with a thickness of 5 ⁇ m, which contains 0.6% ®Omyalite (calcium carbonate from Omya, Switzerland) with an average particle size of 1.2 ⁇ m, an R a value of 60 nm.
• the same recipes are used to produce a 1.4 ⁇ m thick film, an R a value of 35 nm ⁇ 5 nm is obtained.
• the standard viscosity SV (DCE) of the film measured in dichloroacetic acid according to DIN 53728, generally ranges from 700 to 1100, preferably from 800 to 980.
• the film also contains a degassing-resistant hydrolysis stabilizer, which is preferred dosed directly into the film production using the so-called masterbatch technology , the proportion of the hydrolysis stabilizer in the range from 0.2 to 10.0% by weight, preferably from 1.0 to 4.0% by weight, based on the weight of the thermoplastic.
• the proportion of the hydrolysis stabilizer in the master batch is generally from 5.0 to 60.0% by weight, preferably 10.0 to 50.0% by weight, in each case based on the total weight of the master batch.
• Block copolymers are preferred in which Y in formula (II) is a block based 2,4,6-triisopropylphenyl-1,3-diisocyanate or 3,3 ', 5,5'-tetraisopropyl-4,4'-diisocyanatodiphenylmethane means. Mixtures of the compounds mentioned are also suitable.
• Polymeric carbodiimides of the formula (III) are also suitable.
• R 1 , R 2 and R 4 are the same and represent a hydrocarbon radical of the formula C P H (2P + 1) , where p is an integer ⁇ 3, preferably ⁇ 5, and n ⁇ 12, and R 3 is hydrogen ,
• Carbodiimides of the formula (III) whose structure is based on naphthalene rings are also suitable.
• R 5 to R 8 can also be hydrogen or hydrocarbon radicals of the formula C r H (2r + 1) , where r 10 10.
• R 5 and R 6 are the same or different and represent a hydrocarbon radical C r H (2r + 1) , while the remaining radicals are hydrogen.
• the hydrolysis stabilizer is preferably made using masterbatch technology added. To do this, it is first fully dispersed in a carrier material. As Backing material comes from the thermoplastic itself, e.g. the polyethylene terephthalate or other polymers that are compatible with the thermoplastic are also possible. After Dosing to the thermoplastic for the film production melt the components of the masterbatch during the extrusion and are thus dissolved in the thermoplastic.
• a carrier material e.g. the polyethylene terephthalate or other polymers that are compatible with the thermoplastic are also possible.
• the masterbatch can also be produced in-situ, i.e. the monomers for Production of the thermoplastic is carried out together with the other components, e.g. the Hydrolysis stabilizers and / or the compounds mixed to achieve the roughness and the resulting mixtures are polycondensed.
• the monomers for Production of the thermoplastic is carried out together with the other components, e.g. the Hydrolysis stabilizers and / or the compounds mixed to achieve the roughness and the resulting mixtures are polycondensed.
• the layer capacitors produced from the films according to the invention have also statistically fewer columns than those using commercial ones Stabilizers were produced.
• the film can also contain other components such as Flame retardants and / or radical scavengers and / or other polymers such as polyetherimides contain.
• the economic production includes that the raw materials or Raw material components, which are required for the production of the film, with commercially available Industrial dryers such as vacuum dryers (i.e. under reduced pressure), fluid bed dryers or fixed bed dryers (shaft dryers) can be dried.
• Industrial dryers such as vacuum dryers (i.e. under reduced pressure), fluid bed dryers or fixed bed dryers (shaft dryers) can be dried.
• Essential is that the raw materials used according to the invention do not stick together and not thermally be dismantled.
• the dryers mentioned generally work at normal pressure with temperatures between 100 and 170 ° C, where according to the prior art stable against hydrolysis Equipped raw materials can stick and the dryer and / or extruder enforce.
• With a vacuum dryer that allows the gentlest drying conditions the raw material goes through a temperature range of approx. 30 ° C to 130 ° C at a reduced pressure of 50 mbar.
• the film according to the invention is generally produced by extrusion processes known per se manufactured.
• the temperature at which the drawing is carried out can be in a relatively large Range vary and depends on the desired properties of the film.
• the longitudinal and transverse stretching at TG + 10 ° C to TG + 60 ° C glass temperature of the film).
• the aspect ratio is generally in the range from 2.0: 1 to 6.0: 1, preferably from 3.0: 1 to 4.5: 1.
• the transverse stretching ratio is generally in the range of 2.0: 1 to 5.0: 1, preferably 3.0: 1 to 4.5: 1 and that of the possibly carried out second longitudinal and transverse stretching is enclosed 1.1: 1 to 5.0: 1.
• the first longitudinal stretching can optionally be carried out simultaneously with the transverse stretching (simultaneous stretching) be performed. It has proven to be particularly favorable if that Elongation ratio in the longitudinal and transverse directions is in each case greater than 3.5.
• the film In the subsequent heat setting, the film is held at about 0.1 to 10 s Temperature kept from 180 ° C to 260 ° C, preferably 220 to 245 ° C. Subsequently at or starting in heat setting, the film is reduced by 0 to 15%, preferably relaxed by 1.5 to 8% in the transverse and possibly also in the longitudinal direction and the film is cooled and wound up in the usual way.
• the relaxation For the manufacture of SMD processes suitable capacitors, the relaxation must be at least 6%, and at least 2% relaxation must take place at temperatures below 190 ° C.
• the wound film is then processed in conventional metallization machines (e.g. from Applied Films, formerly Leybold) metallized by the known methods (is a coating with another conductive material such as conductive polymers also possible) and assembled in the desired width for capacitor production.
• Condenser coils are made from these metallized narrow cuts, then pressed flat (temperatures between 0 and 280 ° C), looped and contacted.
• the foils are therefore suitable particularly good for the production of capacitors, preferably starter capacitors and SMD solderable interference suppression capacitors. So show these capacitors Passage of high current flows no higher failure rates in the voltage test and in their lifespan.
• the individual are measured Properties in accordance with the standards or procedures listed.
• the standard viscosity SV (DCE), based on DIN 53726, is measured at 25 ° C in dichloroacetic acid (DCE).
• the roughness R a of the film is determined according to DIN 4768 with a cut-off of 0.25 mm.
• the dielectric strength is determined according to DIN 53481 at AC voltage (50 Hz) given as the average of 10 measuring points.
• a voltage for 2 seconds is applied to 100 copies of the manufactured capacitors.
• the voltage test is passed for each capacitor if the voltage does not decrease by more than 10% during the two seconds.
• the overall test is passed if a maximum of 2 of the capacitors used fail.
• 100 capacitors are at 125 ° C for 500 hours in an autoclave at 50% rel. Humidity stored and subjected to the voltage test before and after this time. The The test is considered passed if the capacitors used initially enter the Have passed the stress test, fail at most 2 after tempering.
• the capacitance of 100 capacitors with passed voltage test is measured and the capacitors are placed in a 200 ° C oven for 3 minutes. The capacitance is then determined again for each capacitor. The test is considered passed if a capacitance drift (amount of Capacity before test / capacity after test • 100) an unacceptable value of more than 7% occurs.
• the examples below and the comparative examples are each Films of different thickness, which are produced by a known extrusion process were. Capacitors were made from the films obtained.
• Thermoplastic chips were made according to the ratios given in the examples mixed and pre-crystallized in a fluidized bed dryer at 155 ° C. for 1 minute, then dried for 3 hours in a shaft dryer at 150 ° C and at Extruded at 290 ° C.
• the molten polymer was discharged from a nozzle through a Take-off roller pulled off.
• the film was added by a factor of 3.8 in the machine direction Stretched 116 ° C and in a frame at 110 ° C a transverse stretch by a factor of 3.7 carried out.
• the film was then heat-set at 235 ° C. and in the transverse direction for the first time by 5% at temperatures of 220 - 190 ° C and then again by 2% relaxed at 190 - 150 ° C.
• the film was each vapor-coated with an approx. 500 ⁇ strstrm thick aluminum layer, an unmetallized strip of 2 mm width being produced between each 18 mm wide, metallized strip using masking tapes, and the film was then cut into 10 mm wide strips so that at the edge of the 1 mm wide, unmetallized strips (free edge) remained.
• a metal tape was tightened over the top layer with a pressure of 0.1 kg / cm 2 .
• the winding on the wheel was then looped on both sides, coated with a 0.2 mm thick layer of silver and annealed at 195 ° C. for 60 minutes in an oven (flooded with dry nitrogen).
• the metal strip was then removed from the winding wheel and then cut into individual capacitors at a distance of 0.7 cm.
• the melt resistance of the raw materials used was in the range from 25 • 10 7 to 30 • 10 7 ⁇ cm.
• masterbatch 1 has a weight loss of 0.17%
• masterbatch 3 has a weight loss of 0.05%
• masterbatch 5 has a weight loss of 0.1%.
• example Film thickness ( ⁇ m) composition 1 2.0 11.0% by weight of MB2, 10.0% by weight of MB5 and 79.0% by weight R1 2 6.0 8.0% by weight of MB2, 10.0% by weight of MB5 and 82.0% by weight R1 3 6.0 8.0% by weight of MB4, 10.0% by weight of MB3 and 82.0% by weight R2, extrusion temperature 305 ° C, stretching at 141 ° C
• the properties of the films produced can be found in the table below.

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• Engineering & Computer Science (AREA)
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• Manufacture Of Macromolecular Shaped Articles (AREA)
• Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
• Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
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